Yellow dyes of the phtalimidoquinophthalone series

ABSTRACT

New yellow phthalimidoquinophthalones containing halogen which are outstandingly suitable as pigment dyes.

United States Patent 72] Inventor Johannes Dehnert Ludwigshafen, Germany [21] Appl. No. 843,776

[22] Filed July 22, 1969 [45] Patented Nov. 23, 1971 [73] Assignee Badische Anilin- & Soda-Fabrlk Aktiengesellschaft Ludwigshafen (Rhine), Germany [32] Priority July 24, 1968 [33] Germany S4] YELLOW DYES OF THE PHTALIMIDOQUINOPHTHALONE SERIES 2 Claims, No Drawings [52] US. Cl 260/287 R, 100/288 0, 260/288 R, 260/289 QP, 260/346.3 [51] Int. Cl C07d 33/48 [50] Field of Search 260/287 R, 289 QP 56] References Cited UNITED STATES PATENTS 3,301,860 7/l967 Clarke 260/288 QP 3,399,028 8/1968 llly 260/289 OP FOREIGN PATENTS 480,406 12/1969 Switzerland 260/289QP Primary Examiner-Donald G. Daus I Attorney-Johnston, Root, O'Keeffe, Keil, Thompson and YELLOW DYES OFTHE PHTALIMIDOQUINOPHTHALONE SERIES This invention relates to new yellow dyes of the phthalimidoquinophthalone series having the general formula:

where X and Y each denotes a chlorine or bromine atom.

These quinophthalone derivatives are yellow dyes which are outstandingly suitable as pigment dyes because they are insoluble in water and organic solvents, show excellent fastness to light and are unusually resistant to high temperature.

The new dyes may be prepared for example by heating 8- aminoquinaldine at temperatures of 130 to 300 C. with twice the molar amount of tetrachlorophthalic anhydride or tetrabromophthalic anhydride or simultaneously or successively in any sequence with molar amounts of tetrachlorophthalic anhydride and tetrabromophthalic anhydride, preferably in the presence of solvents or diluents which do not react with the starting materials under the reaction conditions and preferably in the presence of zinc chloride.

Since the amino group of S-aminoquinaldine reacts preferentially, the two dyes having a tetrachlorophthaloyl group and a tetrabromophthaloyl group can be prepared by successive reaction with the two tetrahalophthalic anhydrides.

Examples of solvents or diluents which do not react with the starting materials -trichlorobenzene. the conditions of the reaction are: orthodichlorobenzene, 1,2,4-tribhlorobenzene, diphenyl ether, diphenyl or mixtures of these substances.

The procedure in the production of the new dyes may be for example as follows: 8-aminoquinaldine is heated with a tetrahalophthalic anhydride at temperatures of from 130 to 300 C. preferably from 150 to 250 C. It is advantageous for the reaction to be carried out in the presence of one of the said solvents or diluents. An addition of anhydrous zinc chloride has proved to be advantageous because it facilitates or accelerates the reaction. It is advantageous to use an amount of zinc chloride equal to from to 50 percent by weight of 8- aminoquinaldine The reaction is over after from about 2 to 3 hours at temperatures of about 200 C.

The reaction product may be worked up for example by filtering off the dye and washing it with a solvent such as dimethylformamide, N-methylpyrrolidone or ethanol.

lt may also be advantageous to add these solvents to the reaction mixture prior to the cooling and working up of the same. The dyes are then obtained in a particularly pure form. They can be converted into pigments by dissolution in and reprecipitation from concentrated sulfuric acid and/or other methods usual in pigment technology.

The new dyes have high fastnesses, in particular outstanding light fastness, good resistance to high temperature and excellent fastness to solvents. Because of these advantageous properties the new dyes are very suitable as pigments, for example for the production of surface coatings and printing inks and also for the mass coloration of therrnoplastics such as polystyrene. polyvinyl chloride, polyamides, polyesters, polyacrylonitrile, cellulose tn'acetate and cellulose acetate.

The invention is illustrated by the following examples. The parts and percentages specified in the examples are by weight. Parts by volume have the same relation to parts by weight as the liter to the kilogram.

EXAMPLE 1 A mixture of 158 parts of 8-aminoquinaldine. 858 parts of tetrachlorophthalic anhydride. 40 parts of anhydrous zinc chloride and 2000 parts by volume of trichlorobenzene is boiled for 3 hours, steam being allowed to escape through a 5 short air cooler. The boiling temperature at the end is 220 C. Five hundred parts by volume of dimethylformamide is then added and the whole is stirred for an hour under reflux at about 175 C. The product is suction filtered while hot at 150 to 160 C. and the yellow reaction product is washed with 10 1000 parts by volume of dimethylformamide and at the end with ethanol, and dried. The yellow dye having the formula:

is obtained which is yellow pigment having high fastness to light, solvents and high temperature.

EXAMPLE 2 Eight parts of S-aminoquinaldine and 58 parts of tetrabromophthalic anhydride are heated at 200 to 205 C. with two parts of anhydrous zinc chloride and 200 parts by volume of trichlorobenzene for 2 hours while stirring. One hundred parts by volume of dimethylformamide is added and the product filtered at 120 C. The yellow filter cake is washed, first with dimethylformamide and then with alcohol, and dried. The dye obtained as a yellow powder and having the formula:

is a yellow pigment having high fastness to light, solvents and high temperature.

EXAMPLE3 A mixture of 16 parts of 8-aminoquinaldine, 30 parts of tetrachlorophthalic anhydride and 200 parts by volume of EXAMPLE 4 Forty-eight parts of tetrabromophthalic anhydride and 18 parts of 8-aminoquinaldine are heated together with 200 parts by volume of trichlorobenzene for 3 hours at 150 C. while stirring. Thirty parts of tetrachlorophthalic anhydride and four parts of anhydrous zinc chloride are added and the reaction mixture is brought to 205 to 2 10 C. and kept at this temperature for 5 hours. Seventy-five parts by volume of dimethylformamide is added in the course of half an hour, the internal temperature falling to 180 C. After cooling to l30 C., the reaction product is suction filtered, washed with dimethylformamide and alcohol and dried at 100 C. The yellow dye thus obtained the formula:

A mixture of 16 parts 8-aminoquinaldine, l5 parts of tetrachlorophthalic anhydride and g 24 parts of tetrabromophthalic anhydride is heated to C. and this temperature is maintained for 4 hours while stirring with the flask left open. Then another 15 parts of tetrachlorophthalic anhydride and 24 parts of tetrabromophthalic anhydride are added together with five parts of anhydrous zinc chloride. The whole is heated to 2l0 to 220 and kept at this temperature for 4 hours. The reaction product (isolated analogously to example 3) consists of a mixture of the dyes described in examples l, 2, 3 and 4.

I claim:

I A yellow dye having the formula:

where X and Y each denotes a chlorine or bromine atom.

2. The dye having the formula:

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIGN Patent N 3,622,585 Dated November 2% 1971 lnve t fl Johannes Dehnert It is certified that error appears in the above-identified patent and that; said Letters Patent are hereby corrected as shown below:

Column 1, line 38, "-trichlor'obenzene, should read under line 59, "l,2, k-tribhlorobenzene" should read -l,2,4-triohlorobenzene Column line 9, that portion of the formula reading should read line 71, "dimehtylformamide" HO should read dimethylformamide Column lines 15 to 26, the formula should read 0 Y (I I Y \N l Y OH Y Signed and sealed this 16th day of May 1972.

(SEAL) fittest: J

EDWARD M.FLE'ICHER, JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. The dye having the formula: 